High concentrations of HgS, MeHg and toxic gas emissions in thermally affected waste dumps from hard coal mining in Poland.

This study aims to provide numerous environmental research approaches to understand the formation of mineral and organic mercury compounds in self-heating coal waste dumps of the Upper Silesian Coal Basin (USCB). The results are combined with environmental and health risk assessments. The mineralogy comprised accessory minerals in the fine fraction of thermally affected waste, i.e., Hg sulfides, most likely cinnabar or metacinnabar. Moreover, other metals, e.g., Pb, Zn and Cu, were found as sulfide forms. Apart from Hg, the ICP-ES/MS data confirmed the high content of Mn, Zn, Pb, Hg, Cr and Ba in these wastes. The high concentration of available Hg resulted in elevated MeHg concentrations in the dumps. There were no correlations or trends between MeHg concentrations and elemental Hg, TS, TOC, and pH. Furthermore, we did not detect microbial genes responsible for Hg methylation. The organic compounds identified in waste and emitted gases, such as organic acids, or free methyl radicals, common in such burn environments, could be responsible for the formation of MeHg. The concentration levels of gases, e.g., benzene, formaldehyde, NH3, emitted by the vents, reached or surpassed acceptable levels numerous times. The potential ecological and human health risks of these dumps were moderate to very high due to the significant influence of the high Hg concentrations.

Bioelements and mineral matter in human livers from the highly industrialized region of the Upper Silesia Coal Basin (Poland).

Contents of mineral substance, silica, and a range of bioelements and toxic elements (Mg, Na, K, Ca, Ba, Zn, Cr, P Al, Cd, Mn Cu, Ni, Pb, Sr, Fe) in 38 livers of donors from the Upper Silesia Coal Basin (southern Poland) are presented. Elements were determined by inductively coupled plasma-atomic emission spectrometry (ICP-AES) with the exception of silica that was estimated colorimetrically. Concentrations, concentration variability, and correlations between selected liver components determined for the total population are related to donor age, gender, and lesion occurrence. Correlations between particular elements were found using correlation coefficient values and the Fisher transformation. Mineral substance in the livers lies in the range 0.40-5.03 wt%. With increasing donor age, mineral-matter content decreases to a minimum for the 40-60 years of age range. Microbioelement contents show a similar tendency, while microbioelements and toxic elements reach maximum contents in donors aged 60-80 years. All elements show content decreases in livers from the oldest group (>80 years). Silica contents increase with age. Variability of element contents is lowest in the older subpopulations. Livers with lesions show lower element contents and variability. The results are compared to literature data for regions of Poland assumed to be of low pollution and to data from comparable regions in Japan and Hungary. Up to our knowledge, this paper is the first work describing the total contents, as distinct from contents of selected elements, of mineral substance in human livers.

Geochemical characteristics of solid particles deposited on experimental plots established for traffic pollution monitoring in different countries.

The main aim of this research was to identify the mineralogical, morphological, and chemical characteristics of solid particles emitted by vehicular traffic and deposited on special monitoring plots located on the roadside of five countries with different climatic conditions and traffic structure. Within 24 months of exposure, the composition of the matrix used at the monitoring plots changed. Percentage quartz content decreased in all locations, and due to the input from local sources, the share of other mineral phases increased. In some locations, an increase in the share of mineral phases associated with local parent rock and soil erosion was noted (e.g. Helsinki, Böblingen). In other places, material associated with abrasion of the road surface was characteristic (e.g. Gliwice, Opole). The composition of pollutants accumulated at all the monitoring plots was varied, however the common feature was the presence of technogenic magnetic particles in the matrix after exposure. Analyses showed that numerous irregular, angular particles of iron oxides with porous surface, which are carriers for a number of metals and metalloids were present in the samples. Angular iron oxides containing zinc, chromium, and copper are usually considered as non-exhaust traffic emissions. Another type of iron oxides particles found in the samples were magnetic spherules related to exhaust emissions (smaller spherules, < 20 µm). Study of results confirmed the effectiveness of the testing method for roadside pollution monitoring related to currently emitted solid particles accumulated on matrix of known mineral composition.

Technogenic magnetic particles in soils as evidence of historical mining and smelting activity: A case of the Brynica River Valley, Poland.

In the area of Brynica River basin (Upper Silesia, southern Poland) the exploitation and smelting of iron, silver and lead ores was historically documented since early Middle Ages. First investigations showed that metallurgy industry had a large impact from 9th century (AD) until the Second World War. The aim of the study was to use magnetic prospection to detect traces of past mining and ore smelting in Brynica River Valley located in Upper Silesia (southern Poland). The field screening was performed by measurement magnetic susceptibility (κ) on surface and in vertical profiles and was supported locally by gradiometric measurements. Vertical distribution of magnetic susceptibility values was closely associated with the type of soil use. Historical technogenic magnetic particles resulting from exploitation, processing, and smelting of iron, silver, and lead ores were accumulated in the soil layer at the depth 10 to 25cm. They were represented by sharp-edged particles of slag, coke, as well as various mineralogical forms of iron minerals and aggregates composed of carbon particles, aluminosilicate glass, and single particles of metallic iron. The additional geochemical study in adjacent peat bog supported by radiocarbon dating was also performed. The application of integrated geochemical-magnetic methods to reconstruct the historical accumulation of pollutants in the studied peat bog was effective. The magnetic peak, which was pointed out by magnetic analyses, is consistent with the presence of charcoal and pollution from heavy metals, such as Ag, Cd, Cu, Fe, Pb, or Sn. The results of this work will be helpful for the further study of human's impact on the environment related to the historical and even pre-historical ore exploitation and smelting and also used for better targeting the archeological excavations on such areas.

Technogenic Magnetic Particles in Alkaline Dusts from Power and Cement Plants.

During this study, we investigated the mineralogical characterization of technogenic magnetic particles (TMPs) contained in alkaline industrial dust and fly ash emitted by coal burning power plants and cement plants. The reaction of tested dust samples varied between values of pH 8 and pH 12. Their magnetic properties were characterized by measurement of magnetic susceptibility (χ), frequency dependence of magnetic susceptibility (χ(fd)), and temperature dependence of magnetic susceptibility. Mineralogical and geochemical analyses included scanning electron microscopy with energy dispersive spectroscopy, microprobe analysis and X-ray diffraction. The TMPs in fly ash from hard coal combustion have the form of typical magnetic spherules with a smooth or corrugated surface as well as a skeletal morphology, composed of iron oxides (magnetite, maghemite, and magnesioferrite) that occurred in the form of incrustation on the surface of mullite, amorphous silica, or aluminosilicate particles. The TMPs observed in fly ash from lignite combustion have a similar morphological form but a different mineralogical composition. Instead of magnetite and magnesioferrite, maghemite and hematite with lower χ values were the prevailing magnetic minerals, which explains the much lower magnetic susceptibility of this kind of ash in comparison with the ash from hard coal combustion, and probably results from the lower temperature of lignite combustion. Morphology and mineralogical composition of TMPs in cement dust is more diverse. The magnetic fraction of cement dust occurs mostly in the form of angular and octahedral grains of a significantly finer granulation (<20 µm); however, spherules are also present. A very characteristic magnetic form for cement dust is calcium ferrite (CaFe(3)O(5)). The greatest impact on the magnetic susceptibility of cement dust results from iron-bearing additives (often waste materials from other branches of industry), which should be considered the most dangerous to the environment. Stoichiometric analysis of micro-particles confirmed the presence of heavy metals such as Pb, Mn, Cd, and Zn connected with TMPs, which are carriers of magnetic signals in atmospheric dust. Therefore, in some cases, their presence in topsoil when detected by magnetic measurement can be treated as an indicator of inorganic soil contamination.